Photo-patternable gate dielectrics for OFET

ABSTRACT

Articles utilizing polymeric dielectric materials for gate dielectrics and insulator materials are provided along with methods for making the articles. The articles are useful in electronics-based devices that utilize organic thin film transistors.

This application claims the benefit of priority under 35 U.S.C. §119 ofU.S. Provisional Application Ser. No. 62/132,867 filed on Mar. 13, 2015the content of which is relied upon and incorporated herein by referencein its entirety.

FIELD

Embodiments generally relate to polymeric compounds for use asdielectric materials in electronic devices and organic semiconductordevices comprising novel organic dielectric materials.

TECHNICAL BACKGROUND

There is a continued demand for thinner, lighter, and faster portableelectronics devices. In striving to keep up with these demands, devicemakers are constantly looking for new materials that provide not onlythese qualities, but are also mechanically durable enough for theapplication and producible at a reasonable cost. Organic semiconductorand dielectric materials have attracted a great amount of attention inthe research and commercial communities due to their advantages overinorganic materials, such as high mechanical flexibility, lowmanufacturing cost, and light weight.

One particular challenge for polymer transistors is to fabricate anultrathin defect-free gate dielectric layer that also provides ahigh-quality interface with the adjacent semiconductive layer. Thisdielectric layer has to show high dielectric breakdown strength, verylow electrical conductivity, very low interface and bulk trapping ofcarriers, and good stability. This challenge has been met for Si CMOSFET's through thermally-grown dielectrics. SiO₂ is robust, has high filmintegrity and has sufficiently high dielectric breakdown strength forpractical applications. However, in the case of organic devices, therecontinues to be a need to develop organic containing gate dielectricsystems for commercial applications, such as electronic papers, printedlogic circuits and RFID tags etc. Such gate dielectric layers must beeasy to fabricate conformally on a variety of substrates in bothtop-gate and bottom-gate configurations. They also need to exhibit highflexural strength, significant thermal stability, and environmentalresistance.

It has been found that the functionality of organic-material baseddevices is highly dependent on the synergy of the organic materialsused, meaning that often the various organic components need to bedeveloped and optimized in tandem. For example, although there arenumerous insulating polymer systems known, the search for a gatedielectric that can fulfill all of the above requirements is still nottrivial. Furthermore, the gate dielectric polymer must be compatiblewith the overall designated processing scheme of polymer FETs. Forexample, its formation must not destroy earlier formed layers, while ititself has to survive subsequent solvent and thermal processing.Applicants have found that the unmet needs described are met by thepolymers and devices described herein.

SUMMARY

A first aspect comprises an article comprising a substrate having afirst surface and a second surface; an organic semiconductor layer; agate, a source, and a drain electrode; and a dielectric layer; whereinthe dielectric layer comprises a polymer:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl. In some embodiments, the ratio of n:m is about 3:1 to 1:3 andeach R₁ and R₂ are independently, hydrogen, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl. In someembodiments, Linker is a substituted or unsubstituted alkyl orsubstituted or unsubstituted aryl or heteroaryl. In some embodiments,Linker is a substituted or unsubstituted cycloalkyl, aralkyl, ester,ether, alkoxy, alkylthio, or thioalkyl.

In some embodiments, the dielectric polymer has a dielectric breakdownof greater than 1 MV/cm, or is photocurable, photopatternable, orapplicable as a film at a temperature less than about 250° C.

In some embodiments of the first aspect, the organic semiconductor layercomprises a semiconducting small molecule, semiconducting oligomer, orsemiconducting polymer. In some embodiments, the organic semiconductorcomprises a fused thiophene moiety.

The substrate in the first aspect can comprise a strengthened glasssubstrate. In some such cases, the a functional layer may be present onthe side of the glass substrate opposite the dielectric and OSC layers.Such functional layers may be selected from the group consisting of ananti-glare layer, an anti-smudge layer, a self-cleaning layer, ananti-reflection layer, an anti-fingerprint layer, an opticallyscattering layer, an anti-splintering layer, and combinations thereof.

In some embodiments, the article comprises a top-gate thin filmtransistor, photovoltaic device, diode, or display device, such as atop-gate top-contact or top-gate bottom-contact thin film transistor.

A second aspect comprises an article comprising a substrate having afirst surface and a second surface; an organic semiconductor layer; agate, a source, and a drain electrode; a dielectric layer; and anencapsulation layer; wherein the encapsulation layer comprises apolymer:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl. In some embodiments, the ratio of n:m is about 3:1 to 1:3 andeach R₁ and R₂ are independently, hydrogen, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl. In someembodiments, Linker is a substituted or unsubstituted alkyl orsubstituted or unsubstituted aryl or heteroaryl. In some embodiments,Linker is a substituted or unsubstituted cycloalkyl, aralkyl, ester,ether, alkoxy, alkylthio, or thioalkyl.

In some embodiments, the dielectric polymer has a dielectric breakdownof greater than 1 MV/cm, or is photocurable, photopatternable, orapplicable as a film at a temperature less than about 250° C.

In some embodiments of the first aspect, the organic semiconductor layercomprises a semiconducting small molecule, semiconducting oligomer, orsemiconducting polymer. In some embodiments, the organic semiconductorcomprises a fused thiophene moiety.

The substrate in the first aspect can comprise a strengthened glasssubstrate. In some such cases, the a functional layer may be present onthe side of the glass substrate opposite the dielectric and OSC layers.Such functional layers may be selected from the group consisting of ananti-glare layer, an anti-smudge layer, a self-cleaning layer, ananti-reflection layer, an anti-fingerprint layer, an opticallyscattering layer, an anti-splintering layer, and combinations thereof.

In some embodiments, the article comprises a top-gate thin filmtransistor, photovoltaic device, diode, or display device, such as atop-gate top-contact or top-gate bottom-contact thin film transistor.

A third aspect comprises a method of forming an article, comprisingproviding a substrate having a first surface and a second surface;providing an organic semiconductor layer; providing a dielectric layer;and providing a gate, a source, and a drain electrode; wherein thedielectric layer comprises:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl. In some embodiments, the ratio of n:m is about 3:1 to 1:3 andeach R₁ and R₂ are independently, hydrogen, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl. In someembodiments, Linker is a substituted or unsubstituted alkyl orsubstituted or unsubstituted aryl or heteroaryl. In some embodiments,Linker is a substituted or unsubstituted cycloalkyl, aralkyl, ester,ether, alkoxy, alkylthio, or thioalkyl.

In some embodiments, the dielectric polymer has a dielectric breakdownof greater than 1 MV/cm, or is photocurable, photopatternable, orapplicable as a film at a temperature less than about 250° C.

In some embodiments of the first aspect, the organic semiconductor layercomprises a semiconducting small molecule, semiconducting oligomer, orsemiconducting polymer. In some embodiments, the organic semiconductorcomprises a fused thiophene moiety.

The substrate in the first aspect can comprise a strengthened glasssubstrate. In some such cases, the a functional layer may be present onthe side of the glass substrate opposite the dielectric and OSC layers.Such functional layers may be selected from the group consisting of ananti-glare layer, an anti-smudge layer, a self-cleaning layer, ananti-reflection layer, an anti-fingerprint layer, an opticallyscattering layer, an anti-splintering layer, and combinations thereof.

In some embodiments, the article comprises a top-gate thin filmtransistor, photovoltaic device, diode, or display device, such as atop-gate top-contact or top-gate bottom-contact thin film transistor.

In some embodiments, the providing an organic semiconductor layercomprises coating the substrate with the organic semiconductor layer andcoating the organic semiconductor layer with the dielectric layer.Alternatively, in some embodiments, the providing a dielectric layerstep comprises coating the substrate with the dielectric layer andcoating the dielectric layer with the organic semiconductor layer.

In some embodiments, coating comprises sputter coating, atomic layerdeposition, ink jet printing, slot-die printing, dip coating, spincoating, Langmuir-Blodgett deposition, electrospray ionization, directnanoparticle deposition, vapor deposition, chemical deposition, vacuumfiltration, flame spray, electrospray, spray deposition,electrodeposition, screen printing, close space sublimation,nano-imprint lithography, in situ growth, microwave assisted chemicalvapor deposition, laser ablation, arc discharge, gravure printing,doctor blading, spray-coating, slot die coating, or chemical etching.

A fourth aspect comprises a method of forming an article, comprisingproviding a substrate having a first surface and a second surface;providing an organic semiconductor layer; providing a dielectric layer;and providing a gate electrode in contact with the strengthened glasssubstrate and the dielectric layer; and providing a source electrode anda drain electrode; wherein the dielectric layer comprises:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl. In some embodiments, the ratio of n:m is about 3:1 to 1:3 andeach R₁ and R₂ are independently, hydrogen, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl. In someembodiments, Linker is a substituted or unsubstituted alkyl orsubstituted or unsubstituted aryl or heteroaryl. In some embodiments,Linker is a substituted or unsubstituted cycloalkyl, aralkyl, ester,ether, alkoxy, alkylthio, or thioalkyl.

In some embodiments, the dielectric polymer has a dielectric breakdownof greater than 1 MV/cm, or is photocurable, photopatternable, orapplicable as a film at a temperature less than about 250° C.

In some embodiments of the first aspect, the organic semiconductor layercomprises a semiconducting small molecule, semiconducting oligomer, orsemiconducting polymer. In some embodiments, the organic semiconductorcomprises a fused thiophene moiety.

The substrate in the first aspect can comprise a strengthened glasssubstrate. In some such cases, the a functional layer may be present onthe side of the glass substrate opposite the dielectric and OSC layers.Such functional layers may be selected from the group consisting of ananti-glare layer, an anti-smudge layer, a self-cleaning layer, ananti-reflection layer, an anti-fingerprint layer, an opticallyscattering layer, an anti-splintering layer, and combinations thereof.

In some embodiments, the article comprises a top-gate thin filmtransistor, photovoltaic device, diode, or display device, such as atop-gate top-contact or top-gate bottom-contact thin film transistor.

In some embodiments, the providing an organic semiconductor layercomprises coating the substrate with the organic semiconductor layer andcoating the organic semiconductor layer with the dielectric layer.Alternatively, in some embodiments, the providing a dielectric layerstep comprises coating the substrate with the dielectric layer andcoating the dielectric layer with the organic semiconductor layer.

In some embodiments, coating comprises sputter coating, atomic layerdeposition, ink jet printing, slot-die printing, dip coating, spincoating, Langmuir-Blodgett deposition, electrospray ionization, directnanoparticle deposition, vapor deposition, chemical deposition, vacuumfiltration, flame spray, electrospray, spray deposition,electrodeposition, screen printing, close space sublimation,nano-imprint lithography, in situ growth, microwave assisted chemicalvapor deposition, laser ablation, arc discharge, gravure printing,doctor blading, spray-coating, slot die coating, or chemical etching.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart showing a CV curve of a MIS structure with a 347 nmthick film of epoxy (Formulation 1) showing ˜6 V hysteresis with CCWrotation, and traps near VB and CB edge.

FIG. 2 is an optical micrograph (100× magnification) of a bottom gate,bottom contact TFT on PEN substrate using an epoxide dielectric asdescribed herein for both the gate insulator and passivation layers,along with a fused thiophene organic semiconductor.

FIG. 3 shows the forward and reverse sweeps of I_(d) vs. V_(g) for theTFT on PEN shown in FIG. 2.

FIG. 4 is a cyclic voltammogram (C-V) of Sample D.

FIG. 5 is an example of a of bottom gate-bottom contact OTFT on PENusing an Al gate, a photocured epoxide gate insulator (e.g., Sample H),an Ag source/drain, an organic semiconductor (e.g., PTDC16DPPTDC17FT4),and a photo-patterned epoxide passivation used to mask a channel for dryetching.

DETAILED DESCRIPTION

The present embodiments can be understood more readily by reference tothe following detailed description, drawings, examples, and claims, andtheir previous and following description. However, before the presentcompositions, articles, devices, and methods are disclosed anddescribed, it is to be understood that this description is not limitedto the specific compositions, articles, devices, and methods disclosedunless otherwise specified, as such can, of course, vary. It is also tobe understood that the terminology used herein is for the purpose ofdescribing particular aspects only and is not intended to be limiting.

The following description is provided as an enabling teaching. To thisend, those skilled in the relevant art will recognize and appreciatethat many changes can be made to the various embodiments describedherein, while still obtaining the beneficial results. It will also beapparent that some of the desired benefits can be obtained by selectingsome of the features without utilizing other features. Accordingly,those who work in the art will recognize that many modifications andadaptations to the present embodiments are possible and can even bedesirable in certain circumstances and are a part of the presentdescription. Thus, the following description is provided as illustrativeand should not be construed as limiting.

The term “alkyl” refers to a monoradical branched or unbranchedsaturated hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19 20, 30 or 40 carbon atoms, typically 1-20carbon atoms, more typically from 1 to 10 carbon atoms or 10 to 20carbon atoms. This term is exemplified by groups such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-hexyl, n-decyl,tetradecyl, and the like.

The term “substituted alkyl” refers to: (1) an alkyl group as definedabove, having 1, 2, 3, 4 or 5 substituents, typically 1 to 3substituents, selected from the group consisting of alkenyl, alkynyl,alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino,aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, ester, ether,aralkyl, thioalkyl, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl,arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl,aryloxy, heteroaryl, aminosulfonyl, aminocarbonyl amino, heteroaryloxy,heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,—SO-alkyl, —SO-aryl, —SO— heteroaryl, —SO₂-alkyl, SO₂-aryl and—SO₂-heteroaryl. Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1, 2, or 3substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl,hydroxy, alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(p)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and p is 0,1 or 2; or (2) an alkyl group as defined above that is interrupted by1-10 atoms independently chosen from oxygen, sulfur and NR_(a), whereR_(a) is chosen from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, aryl, heteroaryl and heterocyclyl. All substituents may beoptionally further substituted by alkyl, alkoxy, halogen, CF₃, amino,substituted amino, cyano, or —S(O)_(p)R_(SO), in which R_(SO) is alkyl,aryl, or heteroaryl and p is 0, 1 or 2; or (3) an alkyl group as definedabove that has both 1, 2, 3, 4 or 5 substituents as defined above and isalso interrupted by 1-10 atoms as defined above.

The term “alkoxy” refers to the group D-O—, where D is an optionallysubstituted alkyl or optionally substituted cycloalkyl, or D is a group—Y—W, in which Y is optionally substituted alkylene and W is optionallysubstituted alkenyl, optionally substituted alkynyl; or optionallysubstituted cycloalkenyl, where alkyl, alkenyl, alkynyl, cycloalkyl andcycloalkenyl are as defined herein. Typical alkoxy groups are optionallysubstituted alkyl-O— and include, by way of example, methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy,n-hexoxy, 1,2-dimethylbutoxy, trifluoromethoxy, and the like.

The term “alkylene” refers to a diradical of a branched or unbranchedsaturated hydrocarbon chain, having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, typically 1-10 carbonatoms, more typically 1, 2, 3, 4, 5 or 6 carbon atoms. This term isexemplified by groups such as methylene (—CH₂—), ethylene (—CH₂CH₂—),the propylene isomers (e.g., —CH₂CH₂CH₂— and —CH(CH₃)CH₂—) and the like.

The term “alkylthio” refers to the group R_(S)—S—, where R_(S) is as Dis defined for alkoxy.

The term “alkenyl” refers to a monoradical of a branched or unbranchedunsaturated hydrocarbon group typically having from 2 to 20 carbonatoms, more typically 2 to 10 carbon atoms and even more typically 2 to6 carbon atoms and having 1-6, typically 1, double bond (vinyl). Typicalalkenyl groups include ethenyl or vinyl (—CH═CH₂), 1-propylene or allyl(—CH₂CH═CH₂), isopropylene (—C(CH₃)═CH₂), bicyclo[2.2.1]heptene, and thelike. In the event that alkenyl is attached to nitrogen, the double bondcannot be alpha to the nitrogen.

The term “alkynyl” refers to a monoradical of an unsaturatedhydrocarbon, typically having from 2 to 20 carbon atoms, more typically2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms andhaving at least 1 and typically from 1-6 sites of acetylene (triplebond) unsaturation. Typical alkynyl groups include ethynyl, (—CCH),propargyl (or prop-1-yn-3-yl, —CH₂CCH), and the like. In the event thatalkynyl is attached to nitrogen, the triple bond cannot be alpha to thenitrogen.

The term “aminocarbonyl” refers to the group —C(O)NR_(N)R_(N) where eachR_(N) is independently hydrogen, alkyl, aryl, heteroaryl, heterocyclylor where both R_(N) groups are joined to form a heterocyclic group(e.g., morpholino). Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1-3 substituentschosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy,alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(p)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and p is 0,1 or 2.

The term “acylamino” refers to the group —NR_(NCO)C(O) R_(a) where eachR_(NCO) is independently hydrogen, alkyl, aryl, heteroaryl, orheterocyclyl and R_(a) is chosen from hydrogen, alkyl, cycloalkyl,alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and heterocyclyl.Unless otherwise constrained by the definition, all substituents mayoptionally be further substituted by 1-3 substituents chosen from alkyl,carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃,amino, substituted amino, cyano, and —S(O)_(p)R_(SO), where R_(SO) isalkyl, aryl, or heteroaryl and p is 0, 1 or 2.

The term “acyloxy” refers to the groups —O(O)C-alkyl, —O(O)C-cycloalkyl,—O(O)C-aryl, —O(O)C-heteroaryl, and —O(O)C-heterocyclyl. Unlessotherwise constrained by the definition, all substituents may beoptionally further substituted by alkyl, carboxy, carboxyalkyl,aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino, substituted amino,cyano, and —S(O)_(p)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryland p is 0, 1 or 2.

The term “aryl” refers to an aromatic carbocyclic group of 6 to 20carbon atoms having a single ring (e.g., phenyl) or multiple rings(e.g., biphenyl), or multiple condensed (fused) rings (e.g., naphthyl oranthryl). Typical aryls include phenyl, naphthyl and the like.

Unless otherwise constrained by the definition for the aryl substituent,such aryl groups can optionally be substituted with from 1 to 5substituents, typically 1 to 3 substituents, selected from the groupconsisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl,acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino,azido, cyano, halogen, ester, ether, aralkyl, thioalkyl, hydroxy, keto,thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio,heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl,aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl,heterocyclooxy, hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-aryl,—SO-heteroaryl, —SO₂-alkyl, SO₂-aryl and —SO₂-heteroaryl. Unlessotherwise constrained by the definition, all substituents may optionallybe further substituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(p)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and p is 0, 1 or 2.

The term “aryloxy” refers to the group aryl-O— wherein the aryl group isas defined above, and includes optionally substituted aryl groups asalso defined above. The term “arylthio” refers to the group aryl-S—,where aryl is as defined as above.

The term “amino” refers to the group —NH₂.

The term “substituted amino” refers to the group —NR_(w)R_(w) where eachR_(w) is independently selected from the group consisting of hydrogen,alkyl, cycloalkyl, carboxyalkyl (for example, benzyloxycarbonyl), aryl,heteroaryl and heterocyclyl provided that both R_(w) groups are nothydrogen, or a group —Y—Z, in which Y is optionally substituted alkyleneand Z is alkenyl, cycloalkenyl, or alkynyl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(p)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and p is 0, 1 or 2.

The term “carboxyalkyl” refers to the groups —C(O)O-alkyl or—C(O)O-cycloalkyl, where alkyl and cycloalkyl, are as defined herein,and may be optionally further substituted by alkyl, alkenyl, alkynyl,alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(p)R_(SO), in which R_(SO) is alkyl, aryl, or heteroaryl and p is0, 1 or 2.

The term “cycloalkyl” refers to carbocyclic groups of from 3 to 20carbon atoms having a single cyclic ring or multiple condensed rings.Such cycloalkyl groups include, by way of example, single ringstructures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, andthe like, or multiple ring structures such as adamantanyl,bicyclo[2.2.1]heptane, 1,3,3-trimethylbicyclo[2.2.1]hept-2-yl,(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl), or carbocyclic groups to whichis fused an aryl group, for example indane, and the like.

The term “cycloalkenyl” refers to carbocyclic groups of from 3 to 20carbon atoms having a single cyclic ring or multiple condensed ringswith at least one double bond in the ring structure.

The terms “substituted cycloalkyl” or “substituted cycloalkenyl” referto cycloalkyl or cycloalkenyl groups having 1, 2, 3, 4 or 5substituents, and typically 1, 2, or 3 substituents, selected from thegroup consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl,cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl,alkoxycarbonylamino, azido, cyano, halogen, ester, ether, aralkyl,thioalkyl, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,—SO-alkyl, —SO-aryl, —SO-heteroaryl, —SO₂-alkyl, SO₂-aryl and—SO₂-heteroaryl. Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1, 2, or 3substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl,hydroxy, alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(p)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and p is 0,1 or 2.

The term “halogen,” “halide,” or “halo” refers to fluoro, bromo, chloro,and iodo.

The term “acyl” denotes a group —C(O)R_(CO), in which R_(CO) ishydrogen, optionally substituted alkyl, optionally substitutedcycloalkyl, optionally substituted heterocyclyl, optionally substitutedaryl, and optionally substituted heteroaryl.

The term “heteroaryl” refers to a radical derived from an aromaticcyclic group (i.e., fully unsaturated) having 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, or 15 carbon atoms and 1, 2, 3 or 4 heteroatomsselected from oxygen, nitrogen and sulfur within at least one ring. Suchheteroaryl groups can have a single ring (e.g., pyridyl or furyl) ormultiple condensed rings (e.g., indolizinyl, benzothiazolyl, orbenzothienyl). Examples of heteroaryls include, but are not limited to,[1,2,4]oxadiazole, [1,3,4]oxadiazole, [1,2,4]thiadiazole,[1,3,4]thiadiazole, pyrrole, imidazole, pyrazole, pyridine, pyrazine,pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, isoquinoline, quinoline, phthalazine, naphthylpyridine,quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline,phenanthridine, acridine, phenanthroline, isothiazole, phenazine,isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline,triazole, oxazole, thiazole, naphthyridine, and the like as well asN-oxide and N-alkoxy derivatives of nitrogen containing heteroarylcompounds, for example pyridine-N-oxide derivatives.

Unless otherwise constrained by the definition for the heteroarylsubstituent, such heteroaryl groups can be optionally substituted with 1to 5 substituents, typically 1 to 3 substituents selected from the groupconsisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl,acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino,azido, cyano, halogen, ester, ether, aralkyl, thioalkyl, hydroxy, keto,thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio,heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl,aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl,heterocyclooxy, hydroxyamino, alkoxyamino, nitro, —SO— alkyl, —SO-aryl,—SO-heteroaryl, —SO₂-alkyl, SO₂-aryl and SO₂-heteroaryl. Unlessotherwise constrained by the definition, all substituents may optionallybe further substituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(p)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and p is 0, 1 or 2.

The term “heteroaryloxy” refers to the group heteroaryl-O—.

The term “heterocyclyl” refers to a monoradical saturated or partiallyunsaturated group having a single ring or multiple condensed rings,having from 1 to 40 carbon atoms and from 1 to 10 hetero atoms,typically 1, 2, 3 or 4 heteroatoms, selected from nitrogen, sulfur,phosphorus, and/or oxygen within the ring. Heterocyclic groups can havea single ring or multiple condensed rings, and includetetrahydrofuranyl, morpholino, piperidinyl, piperazino, dihydropyridino,and the like.

The term “thiol” refers to the group —SH.

The term “substituted alkylthio” refers to the group —S— substitutedalkyl.

The term “heteroarylthio” refers to the group —S— heteroaryl wherein theheteroaryl group is as defined above including optionally substitutedheteroaryl groups as also defined above.

The term “sulfoxide” refers to a group —S(O)R_(SO), in which R_(SO) isalkyl, aryl, or heteroaryl. “Substituted sulfoxide” refers to a group—S(O)R_(SO), in which R_(SO) is substituted alkyl, substituted aryl, orsubstituted heteroaryl, as defined herein.

The term “sulfone” refers to a group —S(O)₂R_(SO), in which R_(SO) isalkyl, aryl, or heteroaryl. “Substituted sulfone” refers to a group—S(O)₂R_(SO), in which R_(SO) is substituted alkyl, substituted aryl, orsubstituted heteroaryl, as defined herein.

The term “keto” refers to a group —C(O)—R_(a), where R_(a) is chosenfrom hydrogen, or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,aryl, heteroaryl and heterocyclyl, all of which may be optionallysubstituted with 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano.

The term “thiocarbonyl” refers to a group —C(S)—R_(a), where R_(a) ischosen from hydrogen, or alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, aryl, heteroaryl and heterocyclyl, all of which may beoptionally substituted with 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, and cyano.

The term “carboxy” refers to a group —C(O)OH.

The term “ester” refers to a group —OC(O)R_(e) or —C(O)OR_(e), whereR_(e) is chosen from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,aryl, heteroaryl and heterocyclyl, all of which may be optionallysubstituted with 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, and cyano.

The term “ether” refers to a group -alkyl-O-alkyl, where each alkyl isindependently an optionally substituted alkyl group as defined herein.

The term “thioalkyl” refers to a group -alkyl-S—R_(TA) where alkyl is anoptionally substituted alkyl group and R_(TA) is chosen from hydrogen(in some embodiments, e.g., where the Linker group is thioalkyl, R_(TA)cannot be hydrogen), alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,aryl, heteroaryl and heterocyclyl, all of which may be optionallysubstituted with 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, and cyano.

The term “aralkyl” refers to a group -alkyl-aryl-R_(AR) where alkyl isan optionally substituted alkyl group, aryl is an optionally substitutedaryl or heteroaryl group, and R_(AR) is chosen from hydrogen (in someembodiments, e.g., where the Linker group is thioalkyl, R_(TA) cannot behydrogen), alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl,heteroaryl and heterocyclyl, all of which may be optionally substitutedwith 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl,aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino, substituted amino,and cyano.

Disclosed are materials, compounds, compositions, and components thatcan be used for, can be used in conjunction with, can be used inpreparation for, or are embodiments of the disclosed method andcompositions. These and other materials are disclosed herein, and it isunderstood that when combinations, subsets, interactions, groups, etc.of these materials are disclosed that while specific reference of eachvarious individual and collective combinations and permutation of thesecompounds may not be explicitly disclosed, each is specificallycontemplated and described herein. Thus, if a class of substituents A,B, and C are disclosed as well as a class of substituents D, E, and F,and an example of a combination embodiment, A-D is disclosed, then eachis individually and collectively contemplated. Thus, in this example,each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F arespecifically contemplated and should be considered disclosed fromdisclosure of A, B, and C; D, E, and F; and the example combination A-D.Likewise, any subset or combination of these is also specificallycontemplated and disclosed. Thus, for example, the sub-group of A-E,B-F, and C-E are specifically contemplated and should be considereddisclosed from disclosure of A, B, and C; D, E, and F; and the examplecombination A-D. This concept applies to all aspects of this disclosureincluding, but not limited to any components of the compositions andsteps in methods of making and using the disclosed compositions. Thus,if there are a variety of additional steps that can be performed it isunderstood that each of these additional steps can be performed with anyspecific embodiment or combination of embodiments of the disclosedmethods, and that each such combination is specifically contemplated andshould be considered disclosed.

In this specification and in the claims which follow, reference will bemade to a number of terms which shall be defined to have the meaningsdetailed herein.

“Include,” “includes,” or like terms means encompassing but not limitedto, that is, inclusive and not exclusive.

The term “about” references all terms in the range unless otherwisestated. For example, about 1, 2, or 3 is equivalent to about 1, about 2,or about 3, and further comprises from about 1-3, from about 1-2, andfrom about 2-3. Specific and preferred values disclosed forcompositions, components, ingredients, additives, and like aspects, andranges thereof, are for illustration only; they do not exclude otherdefined values or other values within defined ranges. The compositionsand methods of the disclosure include those having any value or anycombination of the values, specific values, more specific values, andpreferred values described herein.

The indefinite article “a” or “an” and its corresponding definitearticle “the” as used herein means at least one, or one or more, unlessspecified otherwise

As used herein, the term “adjacent” can be defined as being in closeproximity. Adjacent structures may or may not be in physical contactwith each other. Unless specifically disclaimed, adjacent structures canhave other layers and/or structures disposed between them.

All references described or disclosed herein are incorporated byreference in their entireties.

Dielectrics

A major challenge for polymer transistors is to fabricate an ultrathindefect-free gate dielectric layer that also has a high-quality interfacewith the adjacent semiconductive layer. This dielectric layer has toshow high dielectric breakdown strength, very low electricalconductivity, very low interface and bulk trapping of carriers, as wellas be molecularly smooth and also be chemically stable and insoluble tothe typical conventional semiconductor processing solvents.Additionally, a good capacitance-voltage characteristic is necessary tominimize the leakage current of the gate dielectric to achieve anefficient formation of an ideal field-effect channel within the organicsemiconductor layer.

In order to provide stability when exposed to various solvents duringdevice fabrication, a polymeric dielectric material would ideally becrosslinked. In such cases, the crosslinking reaction should take placerapidly to facilitate manufacturing processes, and the ability topattern such a crosslinked material would also be highly desirable. Evenassuming the above criteria are met, an additional requirement is thatthe gate dielectric materials are UV-curable, allowing them to bephoto-cured and/or photo-patterned—a necessity to realize printabilityand flexibility in low-cost OFET technologies.

As noted above, although there many insulating polymer systems known,one that can fulfill all of the above requirements and be compatiblewith the other organic materials in an electronic device is not trivial.Examples of systems that have been tried include:

-   -   Polyimide system (115 J. AMER. CHEM. SOC. 8716-21 (1993)) is        based on thermal conversion of a precursor acid to the insoluble        polyimide and is often deposited before the semiconductive        polymer to give a bottom-gate configured device. However, the        conversion requires prolonged curing at high temperatures above        200° C. with the release of water vapor and large volume        shrinkage. The composition described is not radiation curable or        capable of being easily patterned.    -   PMMA system (8 ADV. MATER. 52-54 (1996)) is based on the        solubility of PMMA in ester solvents (such as alkyl acetates)        which do not swell or roughen the interface of the        semiconductive polymer layer, which is often deposited from        aromatic hydrocarbon solvents. Therefore, PMMA can be deposited        subsequent to the formation of the semiconductive polymer layer        to give top-gate configured devices. But, PMMA is not a        crosslinked polymer and this composition is not radiation        curable or patternable.    -   PVP systems (290 SCIENCE 2123-26 (2000), 93 J. APPL. PHYS.        2977-81 (2003)) are based on the solubility of PVP in alcohol        and other polar solvents which again do not swell or roughen the        interface of the semiconductive polymer layer. PVP however        possesses acidic phenolic groups that are hygroscopic and may        degrade channel properties. The material is also not radiation        curable. This leads to insufficient film-forming properties of        the polymer    -   Photoresist systems (77 APPL. PHYS. LETT. 1487-89 (2000), 21        Opt. Mater. 425-28 (2003)) are usually based on negative resist        technology, for example, via photogenerated acid crosslinking of        epoxy or oxetane groups. The crosslinked material is        insolubilized and may be used in bottom- or top-gate        configurations        Unfortunately, all these candidate systems can suffer from poor        dielectric breakdown strength, often considerably less than 1        MV/cm. Further, they cannot be readily deposited to give        ultrathin films that are conformal and pinhole-free. Still        further, with all of these candidate systems it remains to be        seen if the semiconductive polymer/dielectric interface has        sufficient chemical and thermal stability for commercial        applications

In addition to gate insulator, there exists a need for a polymerpassivation or encapsulation layer with the same properties of lowconductivity, high dielectric breakdown strength, high thermal stabilityand low fixed charge. Typically this layer is deposited over the activelayer of a bottom gate transistor to prevent chemical and physicalsorption of charged or dipole species on the back of the device channel.These charged and dipole species can shift threshold voltage orintroduce trap states which can alter or degrade electrical performance.As with gate dielectrics, it is preferred that these passivation orencapsulation materials be formable into thin conformal and pinhole-freefilms which create a high-quality interface with the back channel of thesemiconductor layer.

In view of the above, there still remains a need to obtain new polymerdielectric systems for use in transistors. Preferably, the new polymerdielectric systems should be easy to fabricate in a desired pattern on avariety of substrates and exhibit high flexure strength andenvironmental resistance. Also, they should have low bulk electricalconductivity, high dielectric breakdown strength, high thermalstability, and low fixed charge. Additionally, it is highly advantageousfor the polymers to be formable into a thin, conformal, pinhole-freefilm that can present a high-quality interface with a polymeric,semiconductive layer.

A first aspect comprises photo-curable, epoxide containing polymers foruse in OTFT applications. Embodied photo-curable epoxide polymers may bedescribed generally by the structure:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl.

Specific embodiments of the photo-curable, epoxide containing polymerscontemplated herein include:

where n is an integer of one or greater; m is an integer of one orgreater; the ratio of n:m is from about 20:1 to about 1:20.

Generally, polymers described herein may be synthesized via reactionssuch as:

wherein A′ is an epoxide-containing monomer; B′ is second monomer; n isan integer of one or greater; m is an integer of one or greater; theratio of n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl. Radical initiators include, but are not limited to, AlBN,ACHN, AAPH, etc. Reactions may be done under reflux conditions andreaction temperatures may be from about 25° C. to 150° C., and aremainly a function of solvent and polymerization conditions.

For example, one embodiment of a photo-curable epoxide polymer for usein gate dielectric applications ispoly(glycidylmethacrylate)-co-poly(methylmethacrylate), or PGMA-Co-PMMA(n:m):

Polymers that meet the above criteria are also potentially useful aspolymer passivation or encapsulation layers. The polymers described herehave the following properties making them ideal as dielectric orencapsulation layers for organic semiconductor based devices: 1) theycan be rapidly photo-patterned with no or minimal thermal treatmentusing equipment common to semi-conductor fabrication facilities (i-line,365 nm) to form uniform, pinhole-free surfaces; 2) when cured, they areresistant to solvents and temperatures commonly encountered infabrication of OSC devices with various configurations; 3) they havegood dielectric breakdown strength and also have low residual bulkelectrical conductivity and fixed charge; and 4) they have excellentelectrically insulating properties, which can enable their use asdielectrics.

The processing characteristics of the disclosed compositions are capableof curing in a shorter time than typical compositions, using energydensity <500 mJ/cm² (UV A, EIT) applied by a 1000 W ozone free Xenonlamp delivering 18 mW/cm² intensity (UV A, EIT).

Several advantages of synthesizing these photo-curableepoxide-containing organic polymeric materials functional groups: (a)The molecular weight of these copolymers can be controlled by varyingchain transfer reagents, radical initiators, reaction time, andtemperature; (b) Different monomers in the copolymer synthesis can beused to see their effect to dielectric properties; (c) Different ratiosof two monomers can be used to adjust the dielectric properties; (d) Bycontrolling the identity and ratio of monomers, surface characteristicscan be adjusted to optimize interfacial interaction with the OSCmaterial in bottom gate OFET devices. This can result in enhanced OSCalignment and better device performance.

Among other desirable properties, the polymers or monomers of thepresent teachings can be soluble in common organic solvents but canbecome insoluble in the same solvents after undergoing crosslinking, forexample, photocrosslinking, which gives rise to certain processingadvantages. The crosslinking functionality can allow formation of adensely crosslinked polymeric matrix. Their formulation is photo-curableand photo-patternable.

Another aspect described herein is articles comprising the dielectricpolymers embodied herein. More specifically, articles comprising thedielectric polymers embodied herein may comprise organic thin filmtransistors. OTFTs can be of any structure, including “bottom-gatetop-contact transistor,” “bottom-gate bottom-contact transistor,”“top-gate top-contact transistor,” and “top-gate top-contact transistor”as shown in U.S. Pat. No. 8,901,544, herein incorporated by reference inits entirety. An organic TFT device can include: a glass substrateincluding the adjacent barrier layer (FIG. 5, “GG”). On the barrierlayer, a gate electrode (FIG. 5, “Gate (Al)”), a dielectric layer (FIG.5, “GI”), a drain electrode (FIG. 5, one of “BC (AU)”), a sourceelectrode ((FIG. 5, other of “BC (AU)”), an optional passivation layer(FIG. 5, “PR”) and an organic semiconducting channel layer can beadjacently formed (FIG. 5, “OSC”). These layers can be stacked indifferent sequences to form a laterally or vertically configuredtransistor device with optional layers in between. The organicsemiconducting channel layer includes semiconducting small molecules,oligomers and/or polymers.

In some embodiments, the organic semiconductor layer comprisessemiconducting small molecules, oligomers and/or polymers.Semiconducting small molecules include the polycyclic aromaticcompounds, such as pentacene, anthracene, and rubrene and otherconjugated aromatic hydrocarbons. Polymeric organic semiconductorsinclude, for example, poly(3-hexylthiophene), poly(p-phenylenevinylene), as well as polyacetylene and its derivatives. Generallyspeaking, there are two major overlapping classes of organicsemiconductors—organic charge-transfer complexes and variouslinear-backbone conductive polymers derived from polyacetylene andsimilar compounds, such as polypyrrole, and polyaniline. However,embodiments are not limited in scope to only these types of organicsemiconductors, and, as shown in the examples, are capable of workingwith a broad range of organic semiconductors.

In some embodiments, the organic semiconductor layer comprises a fusedthiophene compound. In some embodiments, the fused thiophene isincorporated into a polymer. Fused thiophenes and fused thiophenepolymers may comprise compounds as described in U.S. Pat. Nos.7,705,108, 7,838,623, 7,893,191, 7,919,634, 8,217,183, 8,278,346, U.S.application Ser. Nos. 12/905,667, 12/907,453, 12/935,426, 13/093,279,13/036,269, 13/660,637, 13/660,529, and U.S. Prov. Appl. Nos.61/617,202, and 61/693,448, all herein incorporated by reference intheir entireties.

Particular examples of fused thiophene compounds that may be usedinclude, but are not limited to,poly[(3,7-diheptadecylthieno[3,2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene-2,6-diyl)(2,2′-bithiophene)-5,5′-diyl](P2TDC17FT4),poly[(3,7-diheptadecylthieno[3,2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene-2,6-diyl)(2,5-dihexadecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)-5,5′-diyl],poly-3, 6-dihexyl-thieno[3,2-b]thiophene (PDC6FT2), poly-3,6-didecanyl-thieno[3,2-b]thiophene (PDC10FT2),poly[(3,7-diheptadecylthieno[3,2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene-2,6-diyl)(1-hexadecyl-3-(1-hexadecyl-2-oxoindol-3-ylidene)indol-2-one-6,6′-diyl)],andpoly[(3,7-diheptadecylthieno[3.2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene-2,6-diyl)(stilbene-1,4′-diyl)],Poly[(3,7-diheptadecylthieno[3,2-b]thieno[2′,34,5]thieno[2,3-d]thiophene-2,6-diyl)(2,5-dihexadecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)-5,5′-diyl](PTDC16DPPTDC17FT4).

In some embodiments, the organic semiconductor layer may comprise one ormore electroluminescent organic compounds. In some embodiments, thesemiconducting small molecules, oligomers and/or polymers of thesemiconductor layer may comprise electroluminescent organic compounds.

In some embodiments, the organic semiconductor layer is formed by suchprocesses as dip coating, spin coating, Langmuir-Blodgett deposition,electrospray ionization, direct nanoparticle deposition, vapordeposition, chemical deposition, spray deposition, screen printing,nano-imprint lithography, gravure printing, doctor blading,spray-coating, slot die coating, ink jet printing, laser deposition,drop casting or chemical etching.

Substrates that can be used in embodiments described herein can compriseany material that meets the necessary device limitations known to thoseof skill in the art. Examples include polymers, papers, and glasses. Insome embodiments, the substrate used is a strengthened glass substrate,such as an alkali-containing glass. In some embodiments, thestrengthened glass substrate comprises an aluminoborosilicate, analkalialuminoborosilicate, an aluminosilicate, an alkalialuminosilicate,or a soda lime glass. In some embodiments, the glass comprises an ionexchanged glass as described in U.S. Prov. Appl. Nos. 61/560,434,61/653,489, and 61/653,485, and U.S. application Ser. Nos. 12/858,490,12/277,573, 13/588,581, 11/888,213, 13/403,756, 12/392,577, 13/346,235,13/495,355, 12/858,490, 13/533,298, 13/291,533, and 13/305,271, all ofwhich are hereby incorporated by reference in their entirety.

The dielectric layer may act as a gate insulator (FIG. 5, “GI”) orencapsulation layer in an electronic device. The gate insulator (orencapsulation layer) can comprise a photo-curable, epoxide containingpolymers described generally by the structure:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl.

The dielectric layer or encapsulation layer may be formed by, forexample, such processes as sputter coating, atomic layer deposition, dipcoating, spin coating, Langmuir-Blodgett deposition, electrosprayionization, direct nanoparticle deposition, vapor deposition, chemicaldeposition, vacuum filtration, flame spray, electrospray, spraydeposition, electrodeposition, screen printing, close space sublimation,nano-imprint lithography, in situ growth, microwave assisted chemicalvapor deposition, laser ablation, arc discharge, gravure printing,doctor blading, spray-coating, slot die coating, or chemical etching.

In some embodiments, the electronic device is a transistor and comprisesgate, drain, and source electrodes. The electrodes can comprise anyconducting material—including for example, metals, conductingsemi-metals, or conducting non-metals. For example, in some embodiments,an electrode may comprise a metal or combination of metals in the formof a coating, wire, sheet, ribbon, micro- or nanoparticle, or mesh.Electrodes may be formed via such processes as sputter coating, atomiclayer deposition, dip coating, spin coating, Langmuir-Blodgettdeposition, electrospray ionization, direct nanoparticle deposition,vapor deposition, chemical deposition, vacuum filtration, flame spray,electrospray, spray deposition, electrode deposition, screen printing,close space sublimation, nano-imprint lithography, in situ growth,microwave assisted chemical vapor deposition, laser ablation, arcdischarge, gravure printing, doctor blading, spray-coating, slot diecoating, or chemical etching.

In some embodiments, the article further comprises an anti-glare layer,an anti-smudge layer, a self-cleaning layer, an anti-reflection layer,an anti-fingerprint layer, an optically scattering layer, ananti-splintering layer, and combinations thereof. Such layers may beincorporated through any number of known processes, such as thosedisclosed in U.S. Patent Publ. Nos. 2011/0129665, 2009/0197048,2009/0002821, 2011/0267697, 2011/0017287, or 2011/0240064, hereinincorporated by reference.

Another aspect comprises methods of forming embodiments, comprising:providing a glass substrate having a first surface and a second surface;providing an organic semiconductor layer; providing a dielectric layer;and providing at least one electrode. As noted above, it is possible viaa number of processes, all incorporated herein, to provide the variouselements described. In some embodiments, providing an organicsemiconductor layer comprises coating the strengthened glass substratewith the organic semiconductor layer and coating the organicsemiconductor layer with the dielectric layer. In some embodiments,providing a dielectric layer comprises coating the glass substrate withthe dielectric layer and coating the dielectric layer with the organicsemiconductor layer.

EXAMPLES Example 1 Gate Dielectric Containing Photo-Curable Polymer withEpoxide Functional Group

A bisepoxide, Synasia S-06E,

is combined with propyleneglycol monomethyl ether acetate and Aceto CPI6976, a cationic photoinitiator composed of a mixture oftriarylsulfonium hexafluoroantiminate salts. The composition, in weightpercent, is:

Formulation 1 (ELN0402-1-1) Component Wt % Synasia S-06E (Filter 0.45μm, PTFE) 18.0 Aceto CPI6976 0.045 Propyleneglycol monomethyl etheracetate 78.0

The gate dielectric is formed from the resulting polymer by spin castingat 1200 rpm for 30 s on a 2″ Si wafer and pre-baking the wafer in a CEE®WAFER BAKE for 60 s at 90° C. and exposing to UV radiation (ORIEL) at500, 2000, or 4000 mJ/cm². The wafer is then baked for 5, 15, or 30 minat 140° C. Nine samples total are made—one at each radiation exposureand bake time. The resulting wafers are soaked in propylene glycolmonomethyl ether acetate (“PGMEA”) for 5 min and then rubbed with acotton swab to observe film integrity. Any film removal constitutes filmfailure. Any wafers that pass the initial test are re-tested by soakingin PGMEA for 5 min and subsequent rubbing with a cotton swab. Ifnecessary, a third iteration of the swab test is done after soaking inPGMEA for 30 min.

The resulting samples all cure well with no difference discerniblebetween the samples. It appears that 500 mJ/cm² with the UV source and a5 min 140° C. post-bake is sufficient to provide an excellent cure.Additional data suggests that a 1 min post-bake is sufficient.

The C-V curve of a metal-insulating-semiconductor (“MIS”) structureformed from Formulation 1 is shown in FIG. 1. A 347 nm thick dielectricof Formulation 1 is formed on n++Si by spin casting at 1000 rpm,pre-baking at 100° C. for 60 s, exposing the sample to 2000 mJ/cm²exposure, and post-baking at 140° C. for 1 min. A 250 nm thick Alelectrode is sputtered and patterned on the substrate by typicallithographic methods. The C-V curve shows a moderate hysteresis of 6 Vand trapping states near valance band and conduction band edges.

Example 2 Synthesis of Photo-Curable Epoxide Group ContainingCo-Polymers

By varying the level of glycidyl methacrylate used in the co-polymerrecipes, the degree of crosslinking of the materials can be adjusted.Alternatively, by varying the acrylic or styrenic co-monomer, thesurface characteristics (and compatibility with OSC material) can bevaried (see general synthesis procedure, supra). The polymers can alsobe crosslinked by mixing with one or more additional epoxide groupcontaining polymers or lower molecular weight polyepoxy materials.Example 2 provides examples of how variation in the co-monomer affectsthe resulting dielectric material.

1. Synthesis of Copolymer PGMA-Co-PMMA (1:1) (Scheme 1):

To a round-bottom flask, glycidyl methacrylate (34.16 g, 240.29 mmol),methyl methacrylate (24.06 g, 240.29 mmol), 58.22 g of toluene, and 2.33g of AIBN are added. The resulting solution is heated to around 65° C.and maintained at that temperature overnight. The whole reaction mixturebecomes gelled and is dissolved in 60 mL of methylene chloride. Theresulting clear solution is added to a stirred hexane solution toprecipitate out the desired product as a white powder. This white powderis further purified by being re-dissolved in THF and being precipitatedout in MeOH. The purified product PGMA-Co-PMMA (1:1) is obtained as anoff-white solid (48.73 g, 84%). ¹H NMR (300 MHz, CD₂Cl₂): δ 4.29 (broadd, 1H), 3.85-3.71 (m, 1H), 3.58 (s, 3H), 3.26-3.14 (m, 1H), 2.86-2.78(m, 1H), 2.66-2.58 (m, 1H), 2.12-0.77 (m, 10H). GPC (THF): Mn=13,722;Mw=30,060; PDI=2.19. This polymer is very soluble in THF and CH₂Cl₂ andit is also fully soluble in 5%/10% (wt %) (−)-ethyl-lactate/PGME—acommon solvent for photo-curing studies. The polymer is insoluble intoluene and hexane. This polymer in suitable formulation isphoto-curable and patternable.

2. Synthesis of Copolymer PGMA-Co-GPPS (1:1) (Scheme 2):

To a round-bottom flask, glycidyl methacrylate (22.04 g, 212 mmol),styrene (30.08 g, 212 mol), 52.12 g of toluene, and 2.08 g of AIBN areadded. The resulting solution is heated to around 65° C. and maintainedat that temperature overnight. The whole reaction mixture became gelledand is dissolved in 60 mL of methylene chloride. The resulting clearsolution is added to a stirred hexane solution to precipitate out thedesired product as a white powder. This white powder is further purifiedby being re-dissolved in THF and being precipitated out in MeOH. Thepurified product PGMA-Co-GPPS (1:1) is obtained as an off-white solid(48.73 g, 84%). ¹H NMR (300 MHz, CD₂Cl₂): δ 7.4-6.6 (m, 5H), 4.4-0.3 (m,13H). GPC (THF): Mn=15,126; Mw=34,398; PDI=2.27. This polymer is solublein THF and CH₂Cl₂ and it is also fully soluble in 5%/10% (wt %)(−)-ethyl-lactate/PGME—a common solvent for photo-curing studies. Thecured polymer is insoluble in toluene. This polymer in suitableformulation is photo-curable and patternable.

Example 3 Gate Dielectric Formulation Containing Internally SynthesizedPGMA-Co-PMMA Polymer

PGMA-CO-PMMA is combined with Propyleneglycol monomethyl ether acetatealong with Aceto CPI6976, a cationic photoinitiator composed of amixture of triarylsulfonium hexafluoroantiminate salts (Formulation 2).

Formulation 2 Component Wt % PGMA-CO-PMMA (Filter 0.45 μm, PTFE) ~18.0or PGMA-Co-GPPS Aceto CPI6976 0.045 Propyleneglycol monomethyl etheracetate 78.0

The gate dielectric is formed from the polymers shown in Example 2 bythe method shown in Example 1. Both copolymer PGMA-Co-PMMA (1:1)(Scheme 1) and copolymer PGMA-Co-GPPS (1:1) (Scheme 2) cure well in theformulated solution and smooth gate dielectric films are obtained foreach.

Example 4 Gate Dielectric Formulation Containing Commercially-AvailablePhoto-Curable Organic Polymeric Materials with Epoxide Functional Groups

Poly[(2-oxiranyl)-1,2-cyclohexanediol]-2-ethyl-2-(hydroxymethyl)-1,3-propanediolether (“Daicel EHPE3150”, Scheme 3) is combined with Daicel GT-401, alow molecular weight tetraepoxide shown in Scheme 3:

along with Irgacure PAG 290, a cationic photoinitiator composed of amixture of triarylsulfonium hexafluoroantiminate salts (FormulationTable 1).

Component A B C D (Wt %) (Wt %) (batch 2) (Wt %) (Wt %) (Wt %) DaicelEHP3150   10%    8%    6%    4% (EEW17) Daicel GT-401    2%   1.6%  1.2%   0.8% (EEW 222) Irgacure PAG 290  0.12%  0.096%  0.072%  0.048%Baker BTS 220 87.88% 90.304% 92.728% 95.152% (PGMEA)

EHP3150 and GT-401 are dissolved in PGMEA in a brown 125 mL PP Nalgenevessel using an acoustic mixer at 30% for 3 min. The vessel is thenplaced on lab rollers and allowed to roll overnight (16+ hours).Subsequently, the photoinitiator is added and dissolved using anacoustic mixer at 30%. The resulting product is filtered through aWhitman 25 mm, GD/X, 0.2 μm PTFE, PP housing into an EPA cleaned amberglass bottle.

The MIS samples for C-V measurements are prepared as follows. An n++Sisubstrate is stripped with 6:1 BOE, treated with UV ozone andsubsequently coated with 150 nm thick epoxide gate insulator. Theepoxide layer is pre-baked for 1 minute on a 90° C. hot plate (to removesolvent), followed by a 300 s exposure at 18 mW/cm² using a broad bandlight source, and then is baked for 5 min on a 140° C. hot plate. 250 nmAl source and drain electrodes are deposited and patterned by contactlithography and wet etched in type A Al etchant. C-V performance is thenmeasured to provide the results in Table 2.

TABLE 2 Ave. thickness Std. Dev. Sample (nm) (nm) Min (nm) Max (nm) GOFE (402-14-3- 455.6 65.3 387.3 605.0 0.9988 b2a) F (568-1-1) 326.7 50.33273.6 439.2 0.9988 G (568-1-2) 231.2 33.61 195.0 302.3 0.9985 H(568-1-3) 147.8 21.82 123.6 191.5 0.9991 I (402-14-3- 427.9 71.54 349.0578.0 0.9987 b3)

Example 5 OFET Device Prepared Using a Photo-Cured Epoxide DielectricPolymer

A bottom gate, bottom contact OTFT is designed as follows: a cleanGorilla® Glass substrate is patterned with an Al gate (thickness ˜100nm) then coated via spin casting with EHP3150 (film thickness of ˜400nm) as a gate insulator. The substrate is then pre-baked at 90° C. for60 s, exposed to UV light (˜20 mW/cm²) for 60 seconds, and annealing at140° C. for 60 min in air. After annealing, a lift-off Au source anddrain (˜40 nm thick) is patterned, then the organic semiconductormaterial, PTDC16 DPPTDC17FT4, is spin cast onto the device. This OSClayer is annealing at from about 150° C.-190° C. for 40 min to providethe final OTFT. Output is shown in FIG. 1.

Example 6 Bottom-Gate, Bottom Contact OTFT

A substrate consisting of PEN laminated to a glass carrier is coatedwith 150 nm epoxide (Sample H) gate insulator for planarization. Theepoxide layer is cured by 300 s exposure at 18 mW/cm² using a broad bandlight source, followed by a post bake of 10 min on a 120° C. hot plate.A 100 nm Al gate is sputter deposited and patterned by contactlithography and wet etched in type A Al etchant. A second epoxide gateinsulator layer is spun and cured as above. Ag source/drain is formed bysputter deposition of 100 nm Ag followed by contact lithography and wetetch in Transcene TFS Ag etchant diluted 1:1 in pH 10 buffer. Followingan HMDS vapor prime at 120° C., a solution of Corning Incorporated's OSCpolymer (PTDC16DPPTDC17FT4) at 5 mg/mL in 6:4 decalin:toluene is spincast and annealed at 120° C. for 60 min in vacuum. After a brief (5 s)low power O₂ plasma treatment to improve adhesion, a third epoxide layeris spin cast as a passivation layer. This is photo-patterned by exposingthe device to UV radiation for 2.5 s at 18 mW/cm², post baking at 150°C. for 1 min, and developing in PGMEA followed by IPA and DI rinses. Thepatterned passivation layer is used to mask the channel. Channelpatterning is accomplished by RIE using Ar—CHF₃—O₂ (FIG. 2). OTFTperformance is I_(on)/I_(off)˜10⁴, saturation mobility 0.02 cm²/V·s withno hysteresis showing in TFT transfer curves (FIG. 3). Devices made withsame process, except channel patterned by RIE with conventionalphotoresist (subsequently removed), exhibit ˜5 V hysteresis in transfercurves.

We claim:
 1. An article comprising: a. a substrate having a firstsurface and a second surface; b. an organic semiconductor layer; c. agate, a source, and a drain electrode; and d. a dielectric layer;wherein the dielectric layer comprises a polymer:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl.
 2. The article of claim 1, wherein the ratio of n:m is about3:1 to 1:3 and each R₁ and R₂ are independently, hydrogen, substitutedor unsubstituted alkyl, substituted or unsubstituted aryl or heteroaryl.3. The article of claim 1, wherein Linker is a substituted orunsubstituted alkyl or substituted or unsubstituted aryl or heteroaryl.4. The article of claim 1, wherein Linker is a substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl.
 5. The article of claim 1, wherein the organic semiconductorlayer comprises a semiconducting small molecule, semiconductingoligomer, or semiconducting polymer.
 6. The article of claim 4, whereinthe semiconducting small molecule, semiconducting oligomer, orsemiconducting polymer comprises a fused thiophene moiety.
 7. Thearticle of claim 1, wherein the dielectric polymer is photocurable,photopatternable, or applicable as a film at a temperature less thanabout 250° C.
 8. The article of claim 1, wherein the dielectric polymerhas a dielectric breakdown of greater than 1 MV/cm.
 9. The article ofclaim 1, wherein the substrate comprises a strengthened glass substrate.10. The article of claim 1, further comprising a functional layer on thesurface opposite of the organic semiconductor layer and dielectric layerof the strengthened glass substrate, wherein the functional layer isselected from an anti-glare layer, an anti-smudge layer, a self-cleaninglayer, an anti-reflection layer, an anti-fingerprint layer, an opticallyscattering layer, an anti-splintering layer, and combinations thereof.11. The article of claim 1, wherein the article comprises a top-gatethin film transistor, photovoltaic device, diode, or display device. 12.The article of claim 11, wherein the article comprises a top-gatetop-contact or top-gate bottom-contact thin film transistor.
 13. Amethod of forming the article of claim 1, comprising: a. providing asubstrate having a first surface and a second surface; b. providing anorganic semiconductor layer; c. providing a dielectric layer; and d.providing a gate, a source, and a drain electrode; wherein thedielectric layer comprises:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl.
 14. The article of claim 13, wherein the ratio of n:m isabout 3:1 to 1:3 and each R₁ and R₂ are independently, hydrogen,substituted or unsubstituted alkyl, substituted or unsubstituted aryl orheteroaryl.
 15. The article of claim 13, wherein Linker is a substitutedor unsubstituted alkyl or substituted or unsubstituted aryl orheteroaryl.
 16. The article of claim 13, wherein Linker is a substitutedor unsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio,or thioalkyl.
 17. The article of claim 13, wherein the organicsemiconductor layer comprises a semiconducting small molecule,semiconducting oligomer, or semiconducting polymer.
 18. The article ofclaim 17, wherein the semiconducting small molecule, semiconductingoligomer, or semiconducting polymer comprises a fused thiophene moiety.19. The article of claim 13, wherein the dielectric polymer isphotocurable, photopatternable, or applicable as a film at a temperatureless than about 250° C.
 20. The article of claim 13, wherein thedielectric polymer has a dielectric breakdown of greater than 1 MV/cm.21. The article of claim 13, wherein the substrate comprises astrengthened glass substrate.
 22. The article of claim 13, furthercomprising a functional layer on the surface opposite of the organicsemiconductor layer and dielectric layer of the strengthened glasssubstrate, wherein the functional layer is selected from an anti-glarelayer, an anti-smudge layer, a self-cleaning layer, an anti-reflectionlayer, an anti-fingerprint layer, an optically scattering layer, ananti-splintering layer, and combinations thereof.
 23. The article ofclaim 13, wherein the article comprises a top-gate thin film transistor,photovoltaic device, diode, or display device.
 24. The article of claim23, wherein the article comprises a top-gate top-contact or top-gatebottom-contact thin film transistor.
 25. The method of claim 13, whereinthe providing an organic semiconductor layer comprises coating thesubstrate with the organic semiconductor layer and coating the organicsemiconductor layer with the dielectric layer.
 26. The method of claim13, wherein the providing a dielectric layer step comprises coating thesubstrate with the dielectric layer and coating the dielectric layerwith the organic semiconductor layer.
 27. The method of claim 13,wherein coating comprises sputter coating, atomic layer deposition, inkjet printing, slot-die printing, dip coating, spin coating,Langmuir-Blodgett deposition, electrospray ionization, directnanoparticle deposition, vapor deposition, chemical deposition, vacuumfiltration, flame spray, electrospray, spray deposition,electrodeposition, screen printing, close space sublimation,nano-imprint lithography, in situ growth, microwave assisted chemicalvapor deposition, laser ablation, arc discharge, gravure printing,doctor blading, spray-coating, slot die coating, or chemical etching.28. A method of forming the article of claim 1, comprising: a. providinga substrate having a first surface and a second surface; b. providing anorganic semiconductor layer; c. providing a dielectric layer; and d.providing a gate electrode in contact with the strengthened glasssubstrate and the dielectric layer; and e. providing a source electrodeand a drain electrode; wherein the dielectric layer comprises:

wherein A is an epoxide-containing monomer; B is second monomer; n is aninteger of one or greater; m is an integer of one or greater; the ratioof n:m is from about 20:1 to about 1:20; and each R₁ and R₂ areindependently, hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl or heteroaryl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aralkyl, ester, alkoxy, thiol,thioalkyl, or halide; and Linker is a substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or heteroaryl, substituted orunsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio, orthioalkyl.
 29. The article of claim 28, wherein the ratio of n:m isabout 3:1 to 1:3 and each R₁ and R₂ are independently, hydrogen,substituted or unsubstituted alkyl, substituted or unsubstituted aryl orheteroaryl.
 30. The article of claim 28, wherein Linker is a substitutedor unsubstituted alkyl or substituted or unsubstituted aryl orheteroaryl.
 31. The article of claim 28, wherein Linker is a substitutedor unsubstituted cycloalkyl, aralkyl, ester, ether, alkoxy, alkylthio,or thioalkyl.
 32. The article of claim 28, wherein the organicsemiconductor layer comprises a semiconducting small molecule,semiconducting oligomer, or semiconducting polymer.
 33. The article ofclaim 17, wherein the semiconducting small molecule, semiconductingoligomer, or semiconducting polymer comprises a fused thiophene moiety.34. The article of claim 18, wherein the dielectric polymer isphotocurable, photopatternable, or applicable as a film at a temperatureless than about 250° C.
 35. The article of claim 28, wherein thedielectric polymer has a dielectric breakdown of greater than 1 MV/cm.36. The article of claim 28, wherein the substrate comprises astrengthened glass substrate.
 37. The article of claim 28, furthercomprising a functional layer on the surface opposite of the organicsemiconductor layer and dielectric layer of the strengthened glasssubstrate, wherein the functional layer is selected from an anti-glarelayer, an anti-smudge layer, a self-cleaning layer, an anti-reflectionlayer, an anti-fingerprint layer, an optically scattering layer, ananti-splintering layer, and combinations thereof.
 38. The article ofclaim 28, wherein the article comprises a top-gate thin film transistor,photovoltaic device, diode, or display device.
 39. The article of claim28, wherein the article comprises a top-gate top-contact or top-gatebottom-contact thin film transistor.
 40. The method of claim 28, whereinthe providing an organic semiconductor layer comprises coating thesubstrate with the organic semiconductor layer and coating the organicsemiconductor layer with the dielectric layer.
 41. The method of claim28, wherein the providing a dielectric layer step comprises coating thesubstrate with the dielectric layer and coating the dielectric layerwith the organic semiconductor layer.
 42. The method of claim 28,wherein coating comprises sputter coating, atomic layer deposition, inkjet printing, slot-die printing, dip coating, spin coating,Langmuir-Blodgett deposition, electrospray ionization, directnanoparticle deposition, vapor deposition, chemical deposition, vacuumfiltration, flame spray, electrospray, spray deposition,electrodeposition, screen printing, close space sublimation,nano-imprint lithography, in situ growth, microwave assisted chemicalvapor deposition, laser ablation, arc discharge, gravure printing,doctor blading, spray-coating, slot die coating, or chemical etching.